Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D37/00—Tools as parts of machines covered by this subclass
  • B21D37/01—Selection of materials
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
  • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
  • B21D22/02—Stamping using rigid devices or tools
  • B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21D37/00—Tools as parts of machines covered by this subclass
  • B21D37/10—Die sets; Pillar guides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0641—Nitrides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0664—Carbonitrides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/24—Vacuum evaporation
  • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
  • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
  • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
  • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers

Definitions

• the present invention relates to a laminated hard film exerting excellent wear resistance and toughness, and a molding die including the above laminated hard film on/above a substrate surface.
• a substrate surface has hitherto been coated with a hard film of TiN, TiCN, TiAlN or the like for the purpose of improving wear resistance of a jig and tool having a cemented carbide, a cermet, a high-speed tool steel, an alloy tool steel or the like as a substrate.
• a hard film of TiN, TiCN, TiAlN or the like for the purpose of improving wear resistance of a jig and tool having a cemented carbide, a cermet, a high-speed tool steel, an alloy tool steel or the like as a substrate.
• the present inventors have proposed a hard film formed by laminating film layers satisfying predetermined composition ratios on/above a substrate surface of a die for forming a steel material represented by high-tensile steel, for example, as shown in Patent Literature 1.
• Patent Literature 1 Japanese Patent No. 4668214
• the present invention has been made in view of the circumstances as described above, and an object thereof is to provide: a laminated hard film further improved in wear resistance and toughness; and a molding die.
• the atomic ratio of Al to a total of Ti, Cr, Al and Si in the layer A and the layer B falls within a range of 0.20 to 0.60.
• Ti in the layer A is at least partially substituted with Zr.
• the molding die further improved in wear resistance and toughness can be realized by including the laminated hard film as described above on/above a substrate surface.
• a molding die including an intermediate layer of CrN having a thickness of 3 to 10 ⁇ m between the above laminated hard film and the above substrate is also preferred. Further, such a molding die exerts excellent properties, not only at room temperature, but also at a high temperature of about 400 to 500°C, so that it is particularly useful as a die to be used for hot forming of a steel material.
• the wear resistance and toughness can be more improved than the conventional monolayer hard film by using a laminated hard film in which layer(s) A showing good wear resistance and layer(s) B showing high toughness are alternately laminated.
• the hard film of the present invention is a laminated hard film in which layer(s) A showing good wear resistance and layer(s) B showing high toughness are alternately laminated.
• the above layer(s) A contain a predetermined amount of Al, thereby exerting wear resistance excellent in sliding properties with a steel material, particularly in a hot forming region where the temperature becomes high, during forming of the steel material on a surface of which scales have been formed.
• the value of c is preferably 0.60 or more, and more preferably 0.65 or more.
• the atomic ratio of Al or the value of c is necessary to be 0.90 or less.
• the value of c is preferably 0.85 or less, and more preferably 0.80 or less.
• Ti in the above layer(s) A may not be contained in the film. However, by allowing Ti to be contained, the hardness of the film is increased to further improve the wear resistance. From such a viewpoint, the atomic ratio of Ti or the value of a is preferably 0.01 or more, and more preferably 0.02 or more. However, when the Ti amount is excessive, the oxidation resistance of the layer(s) A is decreased, particularly during hot forming. Therefore, the atomic ratio of Ti or the value of a is necessary to be 0.10 or less. The value of a is preferably 0.08 or less, and more preferably 0.05 or less.
• the atomic ratio of Cr or the value of b is necessary to be 0.10 or more.
• the value of b is preferably 0.15 or more, and more preferably 0.20 or more.
• the atomic ratio of Cr or the value of b is necessary to be 0.50 or less.
• the value of b is preferably 0.45 or less, and more preferably 0.40 or less.
• a metal element other than Ti, Cr and Al in the above layer(s) A is Si.
• Si is an element effective for increasing the hardness of the film to improve the wear resistance, and is contained as needed.
• the atomic ratio of Si or the value of d is preferably 0.01 or more, and more preferably 0.02 or more.
• the Si amount is excessive, the oxidation resistance of the layers A is decreased. Therefore, the atomic ratio of Si or the value of d is necessary to be 0.05 or less.
• the value of d is preferably 0.04 or less, and more preferably 0.03 or less.
• the layer(s) B constituting the laminated hard film of the present invention are formed of (Cr e Si 1-e )(C y N 1-y ) and satisfy the following relationship, when the atomic ratios of Cr and C are defined as e and y, respectively, 0.90 ⁇ e ⁇ 1.0 , 0 ⁇ y ⁇ 0.5 or formed of (Al f Si 1-f )(C z N 1-z ) and satisfy the following relationship, when the atomic ratios of Al and C are defined as f and z, respectively. 0.90 ⁇ f ⁇ 1.0 , 0 ⁇ z ⁇ 0.5
• the above layer(s) B contain Cr or Al as a metal element, so that the layer(s) B show high toughness. Specifically, the layer(s) B exert such a property that chipping of the film is less likely to occur under high load.
• the atomic ratios of Cr and Al or the values of e and f are both necessary to be 0.90 or more.
• the values of e and f are both preferably 0.93 or more, and more preferably 0.95 or more.
• the above layer(s) B may be formed of only Cr or Al, Cr or Al may be partially substituted with Si.
• Si is an element effective for increasing the hardness of the film to improve the wear resistance, and is contained as needed.
• the atomic ratio of Si or the value of 1-e or 1-f is necessary to be 0.10 or less.
• the value of 1-e or 1-f is preferably 0.07 or less, and more preferably 0.05 or less.
• carbon C is sometimes contained as an impurity in the film, and in this case, a carbide is partially formed.
• the toughness of the layer(s) B is decreased. From such a viewpoint, the atomic ratio of C or the value of y or z is necessary to be 0.5 or less.
• the value of y or z is preferably 0.3 or less, and more preferably 0.1 or less.
• the hard film having both the excellent wear resistance and toughness can be realized by alternately laminating the layer(s) A excellent in the wear resistance and the layer(s) B excellent in the toughness.
• the layer(s) A and the layer(s) B are necessary to be alternately laminated as independent layer(s), not in a state where compositions of the layer(s) A and the layer(s) B are mixed.
• the thickness of each of the layer(s) A and the layer(s) B is necessary to be 2 nm or more.
• the thickness of each of the layer(s) A and the layer(s) B is preferably 5 nm or more, and more preferably 10 nm or more.
• the thickness of each of the layer(s) A and the layer(s) B is necessary to be 100 nm or less.
• the thickness of each of the layer(s) A and the layer(s) B is preferably 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less, and particularly preferably 20 nm or less.
• the thickness of the layer A and that of the layer B are not necessarily the same with each other.
• the thickness of the layer A is 20 nm, and the thickness of the layer B may be changed between 2 to 100 nm.
• the layer(s) B are not necessarily disposed on the substrate side, and the layer(s) A may be present on the substrate side.
• a film structure that the layer(s) A or the layer(s) B which are present on the substrate side are present on the uppermost surface side may be used, and various laminated structures may be adopted depending on the purpose.
• the thickness of the whole laminated hard film or the total thickness is not limited in any way.
• the total thickness of the film is preferably 1 ⁇ m (1,000 nm) or more, and more preferably 2 ⁇ m (2,000 nm) or more.
• an excessive increase in the total thickness of the film causes deterioration of the toughness of the film. Therefore, it is preferably 20 ⁇ m (20,000 nm) or less, more preferably 10 ⁇ m (10,000 nm) or less, and still more preferably 8 ⁇ m (8,000 nm) or less.
• the number of times of laminating of the layers A and the layers B is recommended to be properly controlled so as to satisfy the preferred total thickness described above.
• the number of times of laminating is preferably plural, i.e. 2 or more. From such a viewpoint, it is preferred to make the thickness of each of the layer(s) A and the layer(s) B as thin as possible and to make the number of times of laminating plural.
• the number of times of laminating as used herein is the value determined, when defining the laminating of the layer A and the layer B as that the number of times of laminating is 1.
• the ratios of the elements in each layer of the layer(s) A and the layer(s) B are as described above. However, in the present invention, it has been found that the atomic ratio of Al to the total of the metal elements in the layer(s) A and the layer(s) B, that is, the total of Ti, Cr, Al and Si in the layer(s) A and the layer(s) B, has a large influence on the wear resistance.
• the term "the atomic ratio of Al to the total of Ti, Cr, Al and Si in the layer(s) A and the layer(s) B" is hereinafter sometimes referred to as "the total Al atomic ratio".
• the above total Al atomic ratio falls within a range of 0.20 to 0.60, in order to ensure the more excellent wear resistance.
• the lower limit of the above total Al atomic ratio it is more preferably 0.30 or more, still more preferably 0.35 or more, and yet still more preferably 0.40 or more.
• the upper limit of the above total Al atomic ratio it is more preferably 0.55 or less.
• the above total Al atomic ratio can be calculated in the following manner.
• the laminated hard film of the present invention is described, taking a combination of the following layer A1 and layer B1 as an example.
• the layer A1 and the layer B1 have the same crystal structure.
• Atomic Ratio of Al to Total of Cr and Al Layer A 1 and Layer B 1 1 / ⁇ 3 ⁇ 4 ⁇ c ⁇ q / 1 / ⁇ 3 ⁇ 4 ⁇ c ⁇ q + 1 / ⁇ 3 ⁇ 4 ⁇ 1 ⁇ c ⁇ q + 1 / ⁇ 3 ⁇ 4 ⁇ r
• the combination of CrAlN as the layer A and CrN as the layer B is used.
• the total Al atomic ratio can be determined by performing calculation as described above.
• the crystal structure is unknown, the calculation as described above cannot be performed. Therefore, the formed layer A or layer B is subjected to measurement by EDX, and the total Al atomic ratio may be determined using the measured results.
• Ti in the layer(s) A is at least partially substituted with Zr, thereby further improving the wear resistance of the layer(s) A.
• Such an effect is increased as the amount of Zr to be substituted increases. This is because the film components are oxidized by heat generation during sliding in the case of use as a molding die to form a hard oxide film containing Zr on a surface thereof.
• the ratio of Ti to be substituted with Zr is not particularly limited, it is preferably at least 10% or more to the Ti amount. All of the Ti amount may be substituted with Zr.
• the preferred atomic ratio range of Zr in this case is the same as the range of the above a in the case where Zr is not allowed to be contained and only Ti is allowed to be contained. That is, when Zr is allowed to be contained in place of Ti, the atomic ratio of Zr is preferably 0.01 or more, and more preferably 0.02 or more, to the whole metal elements of the layer(s) A. However, when the Zr amount is excessive, the oxidation resistance of the layer(s) A is decreased, particularly during hot forming. Therefore, the atomic ratio of Zr is preferably 0.10 or less, more preferably 0.08 or less, and still more preferably 0.05 or less.
• the molding die further excellent in the wear resistance and the toughness can be realized by providing the laminated hard film as described above on/above the substrate surface. Further, the molding die of the present invention exerts the excellent properties, particularly also at high temperature, and therefore, is particularly useful as a die to be used for hot forming of a steel material.
• the molding die of the present invention may include a CrN layer having a thickness of 3 to 10 ⁇ m as an intermediate layer between the above laminated hard film and the substrate, namely just on the substrate.
• the thickness of the intermediate layer in this case is preferably 3 ⁇ m or more, from the viewpoint of ensuring the adhesion.
• the intermediate layer is excessively thick, the toughness of the whole film is deteriorated. Therefore, it is preferably 10 ⁇ m or less. More preferably, it is from 5 to 8 ⁇ m.
• the kind of the substrate used in the above molding die is not particularly limited, examples thereof include tungsten-carbide-based cemented carbides such as WC-Co-based alloys, WC-TiC-Co-based alloys, WC-TiC-(TaC or NbC)-Co-based alloys and WC-(TaC or NbC)-Co-based alloys; cermet alloys such as TiC-Ni-Mo-based alloys and TiC-TiN-Ni-Mo-based alloys; high-speed tool steel materials such as SKH51 and SKD61 specified in JIS G 4403 (2006); alloy tool steel materials such as SKS 11 and SKD1 specified in JIS G 4404 (2006); and the like.
• tungsten-carbide-based cemented carbides such as WC-Co-based alloys, WC-TiC-Co-based alloys, WC-TiC-(TaC or NbC)-Co-based alloys and WC-(
• the hard film is formed on/above the substrate surface by using conventional methods such as a physical vapor deposition process (PVD process) and a chemical vapor deposition process (CVD process).
• PVD process is preferably used to form the film, from the viewpoint of the adhesion of the hard film and the like.
• CVD process chemical vapor deposition process
• an ion plating process such as an arc ion plating (AIP) process or a reactive PVD process such as a sputtering process is effective.
• AIP arc ion plating
• PVD reactive PVD
• UBMS unbalanced magnet sputtering
• the component composition of the target is preferably the same as the desired film composition, because the component composition of the target to be used determines the component composition of the film to be formed.
• the film is formed by the arc ion plating process
• examples thereof include, for example, the following conditions.
• the substrate temperature during deposition is preferably 500°C or lower.
• the laminated hard film of the present invention is suitable for use in a molding die because of its excellent wear resistance and toughness. However, it can also be used, for example, as a hard film formed on/above a surface of a cutting tool by taking advantage of its properties.
• Table 1 were formed by an AIP system. At this time, targets corresponding to respective metal parts of layers A and layers B were used as targets. In addition, a fine particle WC-Co-based cemented carbide ball with a diameter of 10 mm, which had the same composition as a fine particle cemented carbide HTi 10 manufactured by Mitsubishi Materials Corporation was used, after a surface thereof was mirror-finished. As for test Nos. 1 to 31 in the following Table 1, CrN films having a thickness of 5 ⁇ m were formed as intermediate layers prior to the formation of the films. Further, as for test No. 32, the film was directly formed on a substrate surface without forming an intermediate layer. [Table 1] Test No.
• the substrate as a body to be treated was heated to a temperature of 400°C by a heater mounted in a chamber of the above AIP system, and cleaning of the substrate surface by Ar ion was performed.
• the cleaning conditions were atmosphere: Ar, pressure: 0.6 Pa, voltage: 500 V and time: 5 min.
• the pressure in the chamber was adjusted to 4 Pa, and an arc discharge was started at a discharge current of 150 A to form a film having a total thickness of about 5 ⁇ m (about 5,000 nm) on the substrate.
• a bias voltage of 50 V was applied to the substrate so that the substrate has a minus potential to an earth potential.
• the targets having compositions of the layers A and the layers B were attached to separate evaporation sources, respectively, and a table on which the substrate was mounted was rotated in the AIP system.
• the target of the layers A was independently discharged in the nitrogen atmosphere or the nitrogen-methane atmosphere for a short period of time to form the layer A on a surface of the above intermediate layer or the substrate surface.
• the target of the layers B was discharged, and thereafter, the table was rotated while concurrently discharging the layers A and the layers B, thereby forming a multilayer film.
• the layer B was formed. However, whichever of the layer A and the layer B may be present on the substrate side, there is slight difference in the properties therebetween.
• the thickness of the layer A, the thickness of the layer B and the number of times of laminating in the multilayer film were adjusted by varying the rotation speed of the table. That is, when the rotation speed is increased, the thickness of the layer A and the thickness of the layer B are decreased, and the number of times of laminating is increased. When the rotation speed is decreased, the thickness of the layer A and the thickness of the layer B are increased, and the number of times of laminating is decreased. As shown in test Nos. 1 to 4 in Table 1 as comparative examples, various monolayer films were also formed in accordance with ordinary procedures.
• a sliding test was performed under the following conditions to evaluate the wear resistance of the films.
• an alumina plate was used as the following plate in place of a steel plate having scales.
• the diameter of a worn part of the ball was measured, and the area corresponding to the diameter was evaluated as the wear amount.
• the case where the wear amount was 0.4 ⁇ m 2 or less was evaluated as excellent in the wear resistance.
• test Nos. 1 to 5, 12, 13, 17, 19, 21, 26 and 31 do not satisfy any one of the requirements specified in the present invention, and at least either of the wear resistance and the toughness is deteriorated. That is, test No. 1 is a conventional TiN monolayer film, and both the wear resistance and the toughness are deteriorated. Test No. 2 is a conventional CrN monolayer film, and the wear resistance is deteriorated.
• Test Nos. 3 and 4 are examples of forming a monolayer type film formed of only the layer A, and both the wear resistance and the toughness are deteriorated.
• Test No. 5 is an example in which the layer A and the layer B are thin in thickness, and the wear resistance is deteriorated.
• Test No. 12 is an example in which the layer A and the layer B are thick in thickness, and the wear resistance is deteriorated.
• Test No. 13 is an example in which the Al amount in the layers A is insufficient, and the wear resistance is deteriorated.
• Test No. 17 is an example in which the Al amount in the layers A is excessive, and the toughness is deteriorated.
• Test No. 19 is an example in which the Al amount in the layers A is insufficient and the Si amount is excessive, and the wear resistance is deteriorated.
• Test No. 21 is an example in which the Ti amount in the layers A is excessive and the Al amount is insufficient, and the wear resistance is deteriorated.
• Test No. 26 is an example in which the Cr amount in the layers B is small and the Si amount is excessive, and the wear resistance is deteriorated.
• Test No. 31 is an example in which the Al amount in the layers B is small and the Si amount is excessive, and the wear resistance is deteriorated.
• the sliding test and the scratch test were performed at room temperature to evaluate the wear resistance and the toughness of the films.
• the temperature is increased, for example, to such a high temperature as about 400 to 500°C, the results are hardly influenced thereby. Therefore, the film of the present invention is excellent also in the properties at the above high temperature.
• Laminated films having compositions shown in the following Table 3 were formed in the same manner as in Example 1.
• CrN films having a thickness of 5 ⁇ m were formed as intermediate layers prior to the formation of the films.
• the film of No. 7 in Table 3 is the same as the film of No. 22 in Table 1.
• the film of No. 10 in Table 3 is the same as the film of No. 27 in Table 1
• the film of No. 12 in Table 3 is the same as the film of No. 28 in Table 1
• the film of No. 14 in Table 3 is the same as the film of No. 25 in Table 1
• the film of No. 16 in Table 3 is the same as the film of No. 30 in Table 1.
• the total Al atomic ratios of the resulting various films were determined from the compositions of the respective layers, lattice constants shown in Table 3 and thicknesses of the respective layers by the method described above. The total Al atomic ratios are shown in Table 3.
• the sliding test was performed in the same manner as in Example 1 to evaluate the wear resistance of the films.
• the scratch test was performed in the same manner as in Example 1 to evaluate the toughness of the films.
• a laminated hard film of the present invention is more enhanced in wear resistance and toughness, and is useful for a jig and tool or a molding die having an cemented carbide, a cermet, a high-speed tool steel, an alloy tool steel or the like as a substrate.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Ceramic Engineering (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Physical Vapour Deposition (AREA)
• Mounting, Exchange, And Manufacturing Of Dies (AREA)
• Cutting Tools, Boring Holders, And Turrets (AREA)

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• 2014
  • 2014-12-26 JP JP2014266487A patent/JP6326367B2/ja active Active
• 2015
  • 2015-09-15 CN CN201580050905.2A patent/CN106715748A/zh active Pending
  • 2015-09-15 EP EP15845389.4A patent/EP3199660A4/de not_active Withdrawn
  • 2015-09-15 KR KR1020177007076A patent/KR20170042705A/ko not_active Ceased
  • 2015-09-15 CA CA2962195A patent/CA2962195A1/en not_active Abandoned
  • 2015-09-15 US US15/512,712 patent/US20170291211A1/en not_active Abandoned

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